Quality control method for sensor and sensor array production

ABSTRACT

A process of making sensors and sensor arrays that provided real time notification of any centerline deviation. Such production process can be adjusted in real time. Thus, large numbers of units can be made—even in millions of per day—with few if any out of specification units being produced. Such process does not require large-scale clean rooms and is easily configurable.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a continuation-in-part of U.S. patent application Ser. No. 17/336,799 filed Jun. 2, 2021, which in turn is a continuation-in-part of U.S. patent application Ser. No. 17/216,729 filed Mar. 30, 2021, which in turn claims priority to U.S. Provisional Application Ser. No. 63/001,604 filed Mar. 30, 2020, the contents of U.S. patent application Ser. No. 17/336,799, U.S. patent application Ser. No. 17/216,729 and U.S. Provisional Application Ser. No. 63/001,604 hereby being incorporated by reference in their entry.

RIGHTS OF THE GOVERNMENT

The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.

FIELD OF THE INVENTION

The present invention relates to a quality control method for sensor and sensor array production.

BACKGROUND OF THE INVENTION

The production of sensor and sensor arrays via roll to roll processes is a rapid production process. As a result, if the process deviates from its centerline target, thousands of out of specification product units can be made in minutes. Current sensors that are used to sense/detect materials such as viruses, bacteria and chemicals are costly to make and/or use. Thus, what is needed is a roll to roll sensor and sensor array production that can make such units quickly, in large numbers—even in millions per day—and yet still provide few if any out of specification units.

Applicants recognized that the source of the problems associated with current sensor and sensory array production was that the notification that the production process had deviated from centerline was to slow. Such recognition led Applicants to develop a process of making sensors and sensor arrays that provided real time notification of any centerline deviation. As a result, Applicants' production process can be adjusted in real time. Thus, large numbers of units can be made—even in millions per day—few if any out of specification units being produced. Such process does not require large-scale clean rooms and is easily configurable.

SUMMARY OF THE INVENTION

A process of making sensors and sensor arrays that provided real time notification of any centerline deviation. Such production process can be adjusted in real time. Thus, large numbers of units can be made—even in millions of per day—with few if any out of specification units being produced. Such process does not require large-scale clean rooms and is easily configurable.

Additional objects, advantages, and novel features of the invention will be set forth in part in the description that follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the present invention and, together with a general description of the invention given above, and the detailed description of the embodiments given below, serve to explain the principles of the present invention.

FIG. 1 is a schematic depicting the process of coating MoS₂ onto patterned metal contacts followed by laser conversion to 2H-phase MoS₂ device.

FIG. 2 is an example laser processed device configuration with deposited MoS₂ on prepatterned metal contacts and subsequent conversion showing in additional detail Metal electrodes (1), Amorphous MoS₂ (2) and Laser crystallized MoS₂ (3)

FIG. 3A is an example of the first unit operation in a roll-to-roll deposition of MoS₂ onto metal patterned substrates with subsequent laser annealing showing Feed roll (1), Main roller (2), Receiving roller (3), MoS₂ sputtering target (4), Laser (5), Metal sputtering target (6) and Flexible glass substrate (7).

FIG. 3B is an example of a second unit operation in a roll-to-roll deposition of MoS₂ onto metal patterned substrates with subsequent laser annealing showing Receiving roll (1), Main roller (2), Feed roll (3), MoS₂ sputtering target (4), Laser (5), Metal sputtering target (6), and Flexible glass substrate (7).

FIG. 3C is an example of a third unit operation in a roll-to-roll deposition of MoS₂ onto metal patterned substrates with subsequent laser annealing showing Feed roll (1), Main roller (2), Receiving roller (3), MoS₂ sputtering target (4), Laser (5), Metal sputtering target (6), and Flexible glass substrate (7).

FIG. 3D is an example of a fourth unit operation in a roll-to-roll deposition of MoS₂ onto metal patterned substrates with subsequent laser annealing showing Receiving roll (1), Main roller (2), Feed roll (3), MoS₂ sputtering target (4), Laser (5), Metal sputtering target (6), and Flexible glass substrate (7).

FIG. 4 is an example of a pattern for the pattern illumination-based annealed, coated substrate's patterned electrical conductive material (2) on a substrate (1) of the present invention.

FIG. 5 is an example of a pattern for the pattern illumination-based annealed, coated substrate's patterned electrical conductive material (2) on a substrate (1) of the present invention.

FIG. 6 is an example of a pattern for the pattern illumination-based annealed, coated substrate's patterned electrical conductive material (2) on a substrate (1) of the present invention.

FIG. 7 is an example of a pattern for the pattern illumination-based annealed, coated substrate's patterned electrical conductive material (2) on a substrate (1) of the present invention.

FIG. 8 is an example of a pattern for the pattern illumination-based annealed, coated substrate's patterned electrical conductive material (2) on a substrate (1) of the present invention.

FIG. 9 is an example of a pattern for the pattern illumination-based annealed, coated substrate's patterned electrical conductive material (2) on a substrate (1) of the present invention.

FIG. 10 is an example of biomolecular interactions with sensor devices to promote specific interactions with a target biomolecule.

FIG. 11A is an example of measurement of mass accumulation rate (concentration of 2,000 ng/mL over time) of a peptide having SEQ. ID 2 terminated with two leucine amino acids to strengthen interactions with the MoS₂ substrate.

FIG. 11B shows attachment of a concentration of 20,000 ng/mL of the peptide having SEQ. ID 2 over time, with washing steps in phosphate buffered saline and water after attachment with little or no mass loss during washing steps.

FIG. 12A is an example of electrical measurements from a sensor device with a laser-illuminated MoS₂-based rectangular sensor area (approximately 250 micrometers by 200 micrometers) with a concentration of influenza A hemagglutinin (HA) monoclonal antibody fragments applied to the surface via pipetting of a solution containing the antibody fragments in a buffer solution. Measurements of relative resistance changes for the indicated concentrations of Influenza A hemagglutinin and also the indicated concentrations of SARS-CoV-2 spike protein are depicted.

FIG. 12B shows the time response of resistance for a sensor device during functionalization with influenza A hemagglutinin (HA) monoclonal antibody fragments and subsequent attachment of influenza A hemagglutinin at the times indicated on the figure.

FIG. 13 depicts a roll to roll fabrication process with in-situ diagnostic tools both at the location of the laser processing as well as another location in the roll post-processing

FIG. 14 shows resonant Raman spectrum taken using a 633 nm laser of laser treated 2H—MoS₂ regions

FIG. 15 depicts a Raman spectrum of laser treated 2H—MoS₂ region

FIG. 16 shows optical images of roll to roll sensor devices.

DETAILED DESCRIPTION OF THE INVENTION Definitions

Unless specifically stated otherwise, as used herein, the terms “a”, “an” and “the” mean “at least one”.

As used herein, the terms “include”, “includes” and “including” are meant to be non-limiting.

As used herein, the words “about,” “approximately,” or the like, when accompanying a numerical value, are to be construed as indicating a deviation as would be appreciated by one of ordinary skill in the art to operate satisfactorily for an intended purpose.

As used herein, the words “and/or” means, when referring to embodiments (for example an embodiment having elements A and/or B) that the embodiment may have element A alone, element B alone, or elements A and B taken together.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.

It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

Process of Making Sensor Comprising Pattern Illumination-Based Annealed Coated Substrate and One or More Functional Molecules

For purposes of this specification, headings are not considered paragraphs and thus this paragraph is paragraph thirty-seven of the present specification. The individual number of each paragraph above and below this paragraph can be determined by reference to this paragraph's number. In this paragraph thirty-seven, Applicants disclose a process of making a sensor or sensor array said process comprising;

-   -   a.) pattern illumination-based annealing a coated substrate         comprising a substrate having a first side and a second side,         -   (i) said substrate's first side comprising; one or more             coatings of patterned electrical conductive material             disposed over said substrate's first side, preferably said             patterned electrical conductive material comprises a             material selected from the group consisting of             poly(3,4-ethylenedioxythiophene),             poly(3,4-ethylenedioxythiophene) polystyrene sulfonate,             poly(pyrrole), polycarbazoles, polyindoles, polyazepines,             Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au, Ag, Cu, and Pt and             mixtures thereof; more preferably said patterned electrical             conductive material comprises a metal selected from the             group consisting of Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au,             Ag, Cu, and Pt and mixtures thereof, most preferably said             metal comprises a metal selected from the group consisting             of Mo, Cr, Ti, Au and mixtures thereof, most preferably said             one or more coatings of patterned electrical conductive             material is a coating of Mo, a coating of Cr and a second             coating of Au over said coating of Cr or a coating of Ti and             a second coating of Au over said coating of Ti; and one or             more chemical coatings disposed over said one or more             coatings of patterned electrical conductive material, said             one or more chemical coatings each independently comprising             a transition metal and an element selected from the group             consisting of hydrogen, carbon, nitrogen, oxygen, sulfur,             selenium, phosphorous and mixtures thereof, preferably said             one or more chemical coatings each independently comprises a             transition metal and an element selected from the group             consisting of oxygen, sulfur, selenium and mixtures thereof,             said one or more chemical coatings each independently             comprising at least one of an amorphous, nanocrystalline,             microcrystalline or crystalline region, preferably said             chemical coatings comprises one or more transition metal             dichalcogenides, preferably said one or more transition             metal dichalcogenides are selected from the group consisting             of MoS₂, W₅₂, MoSe₂, WSe₂, and mixtures thereof;         -   (ii) said substrate's second side optionally comprising one             or more coatings of patterned electrical conductive material             disposed over said substrate's first side, preferably said             patterned electrical conductive material comprises a             material selected from the group consisting of             poly(3,4-ethylenedioxythiophene),             poly(3,4-ethylenedioxythiophene) polystyrene sulfonate,             poly(pyrrole), polycarbazoles, polyindoles, polyazepines,             Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au, Ag, Cu, and Pt and             mixtures thereof; more preferably said patterned electrical             conductive material comprises a metal selected from the             group consisting of Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au,             Ag, Cu, and Pt and mixtures thereof, most preferably said             metal comprises a metal selected from the group consisting             of Mo, Cr, Ti, Au and mixtures thereof, most preferably said             one or more coatings of patterned electrical conductive             material is a coating of Mo, a coating of Cr and a second             coating of Au over said coating of Cr or a coating of Ti and             a second coating of Au over said coating of Ti; and one or             more chemical coatings disposed over said one or more             coatings of patterned electrical conductive material, said             one or more chemical coatings each independently comprising             a transition metal and an element selected from the group             consisting of hydrogen, carbon, nitrogen, oxygen, sulfur,             selenium, phosphorous and mixtures thereof, preferably said             one or more chemical coatings each independently comprises a             transition metal and an element selected from the group             consisting of oxygen, sulfur, selenium and mixtures thereof,             said one or more chemical coatings each independently             comprising at least one of an amorphous, nanocrystalline,             microcrystalline or crystalline region, preferably said             chemical coatings comprises one or more transition metal             dichalcogenides, preferably said one or more transition             metal dichalcogenides are selected from the group consisting             of MoS₂, W₅₂, MoSe₂, WSe₂ and mixtures thereof;     -   said pattern illumination-based annealing comprising using one         or more lasers and/or lamps to achieve at least one of a         chemical change or structural change in at least a portion of at         least one of said one or more chemical coatings on at least one         side of said substrate, and optionally the removal of at least a         portion of said chemical coating on at least one side of said         substrate;     -   b.) optionally, attaching one or more types of functional         molecules and/or one or more complexes comprising one or more         types of functional molecules and one or more target molecules         (as used herein target molecules can be simple molecules or         macromolecules including but not limited to proteins, lipids,         and carbohydrates, target molecules include aromatics, aromatic         halogens, halocarbon, polar aprotics, volatile organic         compounds, hazardous gases, for example, arsenic, radon,         nitrogen dioxide, carbon monoxide, carbon dioxide, carbon         disulfide, ammonia, napthalene, isoprene, terpenes, methanol,         benzyl chloride, hexachloro-1,3-butadiene, tribomomethane,         1,4-dioxane) to at least a portion of said pattern         illumination-based anneal coated substrate, said one or types of         biomaterial being attached to:         -   (i) a pattern illumination-based annealed portion of said             pattern illumination-based anneal coated substrate;         -   (ii) a portion of said pattern illumination-based anneal             coated substrate that is not pattern illumination-based             annealed; or         -   (iii) a portion of said pattern illumination-based anneal             coated substrate that is not pattern illumination-based             annealed and a portion of said pattern illumination-based             anneal coated substrate that is pattern illumination-based             annealed;     -    preferably said one or more types of functional molecules are         attached to a pattern illumination-based annealed portion of         said pattern illumination-based anneal coated substrate         said process being a roll process wherein said coated chemically         substrate is a rolled coated chemically substrate that is         unrolled at least in part, said unrolled chemical coating         portion of said coated substrate being at least in part pattern         illumination-based annealed, said process comprising a quality         control unit comprising one or more diagnostic detectors, said         one or more diagnostic detectors positioned to collect light         that has interacted with said one or more chemical coatings at         the point of and/or after said pattern illumination-based         annealing has occurred, preferably said one or more diagnostic         detectors are each independently an optical camera, an optical         detector, or Raman spectrometer, preferably said quality control         unit comprises at least two diagnostic detectors, at least one         of said diagnostic detectors positioned to collect light that         has interacted with said one or more chemical coatings at the         point of said pattern illumination-based annealing and at least         one of said diagnostic detectors positioned to collect light         that has interacted with said one or more chemical coatings         after said pattern illumination-based annealing has occurred,         preferably said collected light that has interacted with said         one or more chemical coatings at the point of and/or after said         pattern illumination-based annealing has occurred is suppled         prior to said interaction by a laser, an LED or a broadband         light source, preferably at least a portion of said collected         light that has interacted with said one or more chemical         coatings at the point of and/or after said pattern         illumination-based annealing has occurred is suppled prior to         said interaction by said one or more lasers and/or lamps used to         achieve at least one of a chemical change or structural change         in at least a portion of at least one of said one or more         chemical coatings on at least one side of said substrate. Each         of said chemical coatings may be disposed over said one or more         coatings of patterned electrical conductive material via         chemical or physical vapor deposition processes including but         not limited to thermal decomposition of one or more precursor         gases, thermal evaporation, electron beam evaporation, pulsed         laser deposition, magnetron sputtering, pulsed direct current         magnetron sputtering, high power impulse magnetron sputtering,         and/or molecular beam epitaxy.

Applicants disclose a process of making a sensor according to paragraph thirty-seven wherein said one or more functional molecules are biomaterials is selected from the group consisting of peptides, nanozymes, proteins, lipids, carbohydrates and lectins, nucleic acids and mixtures thereof; preferably said biomaterial is selected from the group consisting of peptides, proteins, nucleic acids and mixtures thereof; preferably

-   -   a) said peptides are selected from the group consisting of         assemblies of the 20 most common amino acids interacting with         both target analytes and the sensor surface, and mixtures         thereof. Such interactions may occur via one or a combination of         the mechanisms of hydrogen bonding, Van der Waals forces, and         ionic interactions between charged species. Peptides may         interact with or bind to the sensor surface without         modification, such as the 12-mer peptide having SEQ. ID 1         discovered via peptide panning on the MoS₂ surface.         Alternatively, amino acids or other molecules may be added to         the peptide to promote binding to sensor surfaces or target         molecules for detection, such as the peptide having SEQ. 2         demonstrating enhanced interactions that may include binding to         laser-processed MoS₂ surfaces when terminated with two Leucine         amino acids. Expected trends dictating interaction strength and         even binding of amino acids in peptides to surfaces, such as         hydrophobicity, charge and surface contact, are not always         observed in practice due to changes in conformation when bound         and other factors. Peptides interacting with the sensor surface         may reduce the strength and frequency of nonspecific         interactions with samples containing multiple components and may         also chemically stabilize the sensor surface. Peptides         complementing receptor binding sites for elements of         cell-surfaces, transmembrane proteins, antibodies, and enzymes         provide a means of rapid, inexpensive, and stable         functionalization. For example, the peptide having SEQ. 2 is         known to bind to cardiac troponin (cTnI), which is regarded as a         biomarker for heart tissue damage. When the peptide is         functionalized with two leucine amino acids, binds to both the         laser-processed MoS₂ sensor surface and cTnI. Peptide binding to         targets of interest may include families of peptides bearing a         resemblance to binding regions of monoclonal antibodies. For         medical diagnostics, another peptide having SEQ. ID 3, is known         to bind to alanine aminotransferase, regarded as a biomarker for         liver damage. Additional examples of peptides interacting with         biological targets of interest may include the peptide having         SEQ. ID 4 detecting HIV1 protease, the peptide having SEQ ID 5         detecting trypsin, the peptide having SEQ. ID 6 for detection of         Caspase 3, and the peptide having SEQ. ID 7 for detection of         MMP-7.     -   b.) said nanozymes are selected from the group consisting of         nanomaterials with intrinsic enzyme-like characteristics,         mimicking the catalytic activity of peroxidase, oxidase,         catalase, haloperoxidase, glutathione peroxidase, uricase,         methane monooxygenase, hydrolase, and superoxide dismutase         generally in the form of compound nanoparticles, including         Fe₃O₂, Mn₃O₄, C₁₈Fe₇N₁₈, and mixtures thereof;     -   c.) said proteins are selected from the group consisting of         antibodies, antibody fragments, antibody mimics, single domain         antibodies, and enzymes and mixtures thereof; amino acids or         other molecules may be added or subtracted from these proteins         to promote interactions including binding to sensor surfaces.         Amino acids or other molecules may also be attached or removed         from these proteins to promote interactions between the proteins         and the sensor surface such as binding, or molecules may be         attached to sensor surface to promote interactions including         binding. Fundamental constituents of the 5 types of antibodies         may be digested into fragments to produce fragments interacting         with sensor surfaces allowing maintenance of the binding region         conformation for the desired effect of reducing non-specific         interactions with a sample. Additionally, smaller proteins with         characteristics allowing specific binding to target         biomolecules, analogous to whole antibodies or antibody         fragments, may be modified to interact with sensor surfaces or         the sensor surfaces may modified to interact with antibodies.         Proteins such as antibodies or antibody fragments interacting         with the sensor surface may reduce the strength and frequency of         non-specific interactions with samples containing multiple         components and may also chemically stabilize the sensor surface.         Such interactions may occur via one or a combination of the         mechanisms of covalent bonding, hydrogen bonding, Van der Waals         forces, and ionic interactions between charged species. This         approach of functionalizing sensor surfaces with antibodies or         antibody fragments is suitable for antibodies that bind to         surface proteins on viruses (such as SARS-CoV2, and Influenza         A), bacteria (such as Streptococcus pyogenes), and other         substances such as hormones (such as human chorionic         gonadotropic hormone) and proteins native to the body (e.g.,         cardiac troponin, cTnI) and substances foreign to the body (such         as THC, narcotics). Since antibodies for each of these         substances share the same fundamental structural elements for         digestion into fragments and use on illumination-crystallized         MoS₂ sensor surfaces. Enzymes are another biomolecule suitable         for promotion of specific interactions. For example, the         angiotensin-converting enzyme 2 (ACE2) binds to spike proteins         of the SARS-CoV and SARS-CoV-2 virus. Modification of ACE2         enzyme for strengthening interactions between the enzyme and the         MoS₂ sensor surface could involve attachment of amino acids         and/or other molecules to allow binding to both sensor and         target analyte. Modification could also involve removal of amino         acids and molecules until a region suitable for binding to the         target analyte remains.     -    For electronic sensing, smaller binding molecules generally         lead to higher sensitivity, indicating an advantage to using         smaller molecules.     -   d.) said lipids are selected from the group consisting of lipid         bilayer arrays and liposomes and mixtures thereof including         those used for support of membrane proteins for biosensing     -   e.) said carbohydrates and lectins are selected from the group         consisting of natural carbohydrates including monosaccharides,         oligosaccharides, polysaccharides, or glycoconjugates with         proteins and lipids including glycoproteins, glycolipids, or         proteoglycans, glycosyltransferases and glycosidases and         mixtures thereof; and     -   f.) said nucleic acids are selected from the group consisting of         deoxyribonucleic acid, ribonucleic acid and mixtures thereof to         identify genes and genetic mutations in healthy and diseased         tissue and other biomolecular targets.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through thirty-eight wherein said biomaterial's attachment to said pattern illumination-based anneal coated substrate comprises at least one of a covalent bond, electrostatic bond or a covalent and electrostatic bond. In one aspect, said at least one covalent bond comprises a disulfide bond.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through thirty-nine wherein said attaching said biomaterial's to said pattern illumination-based anneal coated substrate comprises contacting said at least a portion of said pattern illumination-based anneal coated substrate and said one or more types of biomaterials, preferably said contacting said at least a portion of said pattern illumination-based anneal coated substrate with said one or more types of biomaterials comprises contacting said at least a portion of said pattern illumination-based anneal coated substrate with a solution comprising said one or more types of biomaterials, more preferably said contacting said at least a portion of said pattern illumination-based anneal coated substrate with said one or more types of biomaterials comprises contacting at least a portion of said pattern illumination-based anneal coated substrate with a solution comprising said one or more types of biomaterials via at least one of pipetting (manually or with an automated system), spraying, printing, dipping, or any other means of applying a solution to a surface. The biomaterial may be suspended in water or any suitable buffer such as phosphate buffered saline with a concentration of from about 0.0001×PBS to about 100×PBS, preferably from about 0.001×PBS-to about 20×PBS, most preferably from about 0.01×PBS to about 10×PBS, where 1×PBS is a composition of about 137 mM NaCl, 2.7 mM KCl, 10 mM Na₂HPO₄, and 1.8 mM KH₂PO₄, said water or suitable buffer may have, but is not limited to, a pH from about 6.8 to about 7.4. In order to achieve the desired concentration of one or more types of functional molecules per unit of square area on the active sensor region, a solution comprising from about 0.01 pg/mL to about 100 mg/mL of said one or more types of functional molecules may be applied to the active sensor region, preferably in order to achieve the desired concentration of one or more types of functional molecules per unit of square area on the active sensor region, a solution comprising from about 0.1 pg/mL to about 10 mg/mL of said one or more types of functional molecules may be applied to the active sensor region, more preferably in order to achieve the desired concentration of one or more types of functional molecules per unit of square area on the active sensor region, a solution comprising from about 1,000 pg/mL to about 0.1 mg/mL of said one or more types of functional molecules may be applied to the active sensor region, most preferably in order to achieve the desired concentration of one or more types of functional molecules per unit of square area on the active sensor region, a solution comprising from about 100 pg/mL about 1,000 ng/mL of said one or more types of functional molecules may be applied to the active sensor region.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty wherein:

-   -   a.) at least one of said one or more chemical coatings comprises         two or more regions that are amorphous, nanocrystalline,         microcrystalline or crystalline with the proviso that at least         two of said regions are not identical with respect to being         amorphous, nanocrystalline, microcrystalline or crystalline and         said laser or lamp forms on, within or on and within said at         least one of said one or more chemical coatings:         -   (i) at least two electronic elements selected from a             conductor, semiconductor and an insulator;         -   (ii) two or more different conductors having at least one of             the following: different electrical properties or different             optical properties;         -   (iii) two or more different semiconductors having at least             one of the following: different electrical properties or             different optical properties; or         -   (iv) two or more different insulators having at least one of             the following: different electrical properties or different             optical properties;     -   said process being performed under one of the following         conditions: vacuum of less 100 torr, air or under a fluid         blanket other than air;     -   said pattern illumination-based annealing resulting in at least         one of a chemical change or structural change, and the removal         of at least a portion of at least one of said one or more         chemical coatings and resulting in an electrical component, an         optical component or a combined electrical and optical component         being formed on, within or on and within at least a portion of         said pattern illumination-based annealed one or more chemical         coatings; or     -   b) at least one of said one or more chemical coatings comprises         at least one region that is amorphous, nanocrystalline,         microcrystalline or crystalline, and said one or more lasers         and/or lamps forms on, within or on and within said at least one         of said one or more chemical coatings:         -   (i) at least two electronic elements selected from a             conductor, semiconductor and an insulator;         -   (ii) two or more different conductors having at least one of             the following: different electrical properties or different             optical properties;         -   (iii) two or more different semiconductors having at least             one of the following: different electrical properties or             different optical properties; or         -   (iv) two or more different insulators having at least one of             the following: different electrical properties or different             optical properties;     -    said process being performed under one of the following         environmental conditions: vacuum of less than 100 torr, air or         under a fluid blanket other than air, then repeating, one or         more times said pattern illumination-based annealing on said         portion of said one or more chemical coatings using one or more         of the following:         -   (i) the same device but at least one of the following: a             different intensity or time;         -   (ii) a different environmental condition from the previous             environmental condition, said different environmental             condition select from the same group of environmental             conditions; or         -   (iii) a lamp if the previous pattern illumination-based             annealing was laser pattern illumination-based annealing or             a laser if the previous pattern illumination-based annealing             was lamp pattern illumination-based annealing             said pattern illumination-based annealing resulting in at             least one of a chemical change or structural change, and the             removal of at least a portion of at least one of said one or             more chemical coatings and resulting in an electrical             component, an optical component or a combined electrical and             optical component being formed on, within or on and within             at least a portion of said pattern illumination-based             annealed one or more chemical coatings.

Applicants disclose a process of making a sensor according to paragraph forty-one wherein for element b) said at least one chemical coating comprises two or more regions that are amorphous, nanocrystalline, microcrystalline or crystalline with the proviso that at least two of said regions are not identical with respect being amorphous, nanocrystalline, microcrystalline or crystalline, at least two of said regions being pattern illumination-based annealed via different pattern illumination-based annealing processes.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty-two wherein said transition metal is selected from the group consisting of molybdenum, tungsten, niobium, tantalum, vanadium, titanium, chromium, iron, rhodium, hafnium, rhenium and mixtures thereof.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty-three wherein said process is performed under a fluid blanket other than air.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty-three wherein said fluid blanket comprises:

-   -   a) an element selected from the group consisting of krypton,         xenon, radon, argon, neon, helium, hydrogen, carbon, nitrogen,         oxygen, sulfur, selenium, phosphorous and mixtures thereof;     -   b) based on total fluid volume greater than 0% to about 19% or         from 21% to 100% oxygen; and/or     -   c) greater than 0% to about 78% or from 80% to 100% nitrogen.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty-five wherein said material comprises at least one region that is amorphous or nanocrystalline.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty-six wherein said pattern illumination-based annealing is achieved by using one or more lasers, said one or more lasers each being independently selected from a laser that is a pulsed laser, a continuous laser or a pulsed/continuous laser. A pulsed/continuous laser is a laser that can provide a pulsed laser beam and a continuous laser.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty-six wherein said pattern illumination-based annealing is achieved by using a continuous wave laser to subject at least a portion of said chemical coating, for a time of about 0.001 milliseconds to 60 seconds to said continuous laser, preferably for a time of about 0.1 milliseconds to 10 seconds to said continuous laser, more preferably for a time of about 1 millisecond to 1 second to said continuous laser; said continuous laser having power of from about 1 microwatt to about 1 megawatt over the time period said at least a portion of said chemical coating is subjected to said continuous laser, preferably said continuous laser having power of from about 0.1 milliwatt to about 1 kilowatt over the time period said at least a portion of said chemical coating is subjected to said continuous laser, more preferably said continuous laser having power of from about 1 microwatt to about 500 watts over the time period said at least a portion of said chemical coating is subjected to said continuous laser; preferably said portion of said chemical coating has an area of about 100 square nanometers to about 1 square meter, more preferably said portion of said chemical coating has an area of about 1 square micrometer to about 1 cm², most preferably said portion of said chemical coating has an area of about 100 square micrometers to about 250,000 square micrometers. Said portion of said chemical coating may be of any geometry including but not limited to a rectangular, circular or square.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty-six wherein said pattern illumination-based annealing is achieved by using a lamp to subject at least a portion of said chemical coating for a time of about 10 microseconds to about 500,000 microseconds, preferably for a time of about 25 microseconds to about 100,000 microseconds, more preferably for a time of about 50 microseconds to about 1,000 microseconds to said lamp, said lamp having power of from about 0.01 J/cm²to about 1,000 J/cm², preferably said lamp having power of from about 0.1 J/cm² to about 100 J/cm², more preferably said lamp having power of from about 2 J/cm² to about 10 J/cm², preferably said portion of said chemical coating has an area of about 1 square micrometer to about 50 square meters, more preferably said portion has an area of about 1 square micrometers to about 1 square meter, most preferably said portion of said chemical coating has an area of about 10 square micrometers to about 1 cm². Said portion of said chemical coating may be of any geometry including but not limited to a rectangular, circular or square.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through forty-six wherein said pattern illumination-based annealing is achieved by using a pulsed laser to subject at least a portion of said chemical coating for a time of about 0.1 femtoseconds to 60 seconds to said pulsed laser, preferably for a time of about 0.1 nanoseconds to 1 second to said pulsed laser, more preferably for a time of about 10 nanoseconds to 1 millisecond to said pulsed laser; said pulsed laser having a peak power of from about 0.1 microwatt to about 1000 gigawatts over the time period said at least a portion of said chemical coating is subjected to said pulsed laser, preferably said pulsed laser having a peak power of from about 0.1 milliwatt to about 100 megawatts over the time period said at least a portion of said chemical coating is subjected to said pulsed laser, more preferably said pulsed laser having a peak power of from about 1 watt to about 50 megawatts over the time period said at least a portion of said chemical coating is subjected to said pulsed laser; said pulsed laser having a pulse period of about 0.1 femtoseconds to 1 second, preferably said pulsed laser having a pulse period of about 0.1 nanosecond to 1 microsecond, more preferably said pulsed laser having a pulse period of about 1 nanosecond to 100 nanoseconds; preferably said portion of said chemical coating has an area of about 100 square nanometers to about 1 square meter, more preferably said portion of said chemical coating has an area of about 1 square micrometers to about 1 cm², most preferably said portion of said chemical coating has an area of about 100 square micrometers to about 500 square micrometers. Said portion of said chemical coating may be of any geometry including but not limited to a rectangular, circular or square.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through fifty wherein, said each chemical coating independently has a thickness of from about 0.1 nanometers to about 1 centimeter.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through fifty wherein, said each chemical coating independently has a thickness of from about 0.3 nanometers to about 10 micrometers.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through fifty-two wherein, said electrical and/or optical component is selected from the group consisting of an inductor, a capacitor, a resistor, a diode, a transistor, a trace, a battery, an optical filter, a chemical sensor, a biological sensor and a solar cell.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through fifty-three wherein each of said one or more chemical coatings have an area and a thickness and said removal of said at least a portion of said one or more chemical coating occurs, said removal comprising at least one of:

-   -   a.) laser ablation removal of from about 0.1% to about 99.9% of         at least one of said one or more chemical coatings' area,         preferably said removal comprising laser ablation removal of         from about 2% to about 98% of at least one of said chemical         coatings' area, more preferably said removal comprising laser         ablation removal of from about 10% to about 90% of at least one         of said chemical coatings' area; or     -   b.) laser ablation removal of at least 85% of at least one of         said chemical coatings' thickness, preferably said removal         comprises laser ablation removal of at least 95% of at least one         of said chemical coatings' thickness; or laser ablation removal         of about 85% to about 99% of at least one of said chemical         coatings' thickness.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through fifty-four wherein said substrate of said coated substrate is selected from glass, polymer and mixtures thereof, preferably said polymer is selected from the group consisting of polyethylene naphthalate, polyimide, polycarbonate, polyethylene naphthalate and polyethylene terephthalate and mixtures thereof.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through fifty-five wherein at least a portion of said coated substrate's pattern illumination-based annealed chemical coating is further treated by at least one of the following processes:

-   -   a.) two or more pattern illumination-based annealings; said two         more pattern illumination-based annealings may each be         independently conducted in accordance with the process disclosed         in paragraphs thirty-three through fifty-two;     -   b.) plasma treatment comprising exposing said at least a portion         of said coated substrate's pattern illumination-based annealed         chemical coating to an ionized gas derived from the group         consisting of He, Ne, Ar, Kr, Xe, H₂, O₂, SF₆, CF₄, N₂ and         mixtures thereof preferably said plasma treatment comprises         exposing said at least a portion of said coated substrate's         pattern illumination-based annealed chemical coating to an         ionized gas derived from the group consisting of He, Ar, H₂, O₂,         SF₆, CF₄ and mixtures thereof, more preferably said plasma         treatment comprises exposing said at least a portion of said         coated substrate's pattern illumination-based annealed chemical         coating to an ionized gas derived from the group consisting of         Ar, H₂, SF₆, CF₄ and mixtures thereof, most preferably said         plasma treatment comprises exposing said at least a portion of         said coated substrate's pattern illumination-based annealed         chemical coating to an ionized gas derived from the group         consisting of Ar, and mixtures thereof.         -   (i) said plasma treatment being conducted at a pressure of             from about 0.1 mTorr to about 1000 Torr, preferably said             plasma treatment being conducted at a pressure of about 0.5             mTorr to about 760 Torr, more preferably said plasma             treatment being conducted at a pressure of about 1 mTorr to             about 100 Torr, most preferably said plasma treatment being             conducted at a pressure of about 1 mTorr to about 10 Torr;         -   (ii) said at least a portion of said coated substrate's             pattern illumination-based annealed chemical coating's             plasma treatment temperature being from about 0° C. to about             1,500° C., preferably said at least a portion of said coated             substrate's pattern illumination-based annealed chemical             coating's plasma treatment temperature being from about             5° C. to about 1,000° C., more preferably said at least a             portion of said coated substrate's pattern             illumination-based annealed chemical coating's plasma             treatment temperature being from about 5° C. to about 900°             C., most preferably said at least a portion of said coated             substrate's pattern illumination-based annealed chemical             coating's plasma treatment temperature being from about             18° C. to about 700° C.; and         -   (iii) said at least a portion of said coated substrate's             pattern illumination-based annealed chemical coating             exposure time being from about 0.001 seconds to about             10,000,000 seconds, preferably said at least a portion of             said coated substrate's pattern illumination-based annealed             chemical coating exposure time being from about 0.01 seconds             to about 1,000,000 seconds, more preferably said at least a             portion of said coated substrate's pattern             illumination-based annealed chemical coating exposure time             being from about 0.1 seconds to about 100,000 seconds, most             preferably said at least a portion of said coated             substrate's pattern illumination-based annealed chemical             coating exposure time being from about 0.1 seconds to about             10,000 seconds. Different modes of plasma generation may             include remote plasmas from sources such as electron             cyclotron resonance, inductively coupled plasmas,             capacitively coupled plasmas, and electron beam generated             plasmas. Inductively coupled and glow discharge plasmas by             coupling of power to the substrate may also be used alone or             in conjunction with a remote plasma source. Plasma power may             be continuous or pulsed from frequencies ranging from 0.01             Hz to 10 GHz.     -   c.) The ion beam irradiation comprising exposing said at least a         portion of said coated substrate's pattern illumination-based         annealed chemical coating to an ion beam, said ion beam         comprising an ionized gas derived from the group consisting of         He, Ne, Ar, Kr, Xe, H₂, O₂, SF₆, CF₄, N₂ and mixtures thereof;         preferably said ion beam comprises an ionized gas derived from         the group consisting of He, Ar, H₂, O₂, SF₆, CF₄ and mixtures         thereof, more preferably said ion beam comprising an ionized gas         derived from the group consisting of Ar, H₂, SF₆, CF₄ and         mixtures thereof, most preferably said ion beam comprising an         ionized gas derived from the group consisting of Ar, H₂ and         mixtures thereof;         -   (i) said ion beam having an incident ion energy of from             about 50 eV to about 10,000 eV, preferably said ion beam             having an incident ion energy of from about 100 eV to about             5,000 eV, more preferably said ion beam having an incident             ion energy of from about 100 eV to 2000 eV, most preferably             said ion beam having an incident ion energy of from about             100 eV to 1000 eV;         -   (ii) said ion beam having an incoming ion species incident             angle of from about 1° to 90°, relative to the surface being             bombarded, preferably said ion beam having an incoming ion             species incident angle of from about 3° to about 90°, more             preferably said ion beam having an incoming ion species             incident angle of from about 4° to about 90°, and most             preferably said ion beam having an incoming ion species             incident angle of from about 5° to about 90°;         -   (iii) said ion beam having an incident ion flux of from             about 0.1 nA/mm² to about 900,000,000 nA/mm², preferably             said ion beam having an incident ion flux of from about 0.5             nA/mm² to about 10,000,000 nA/mm², more preferably said ion             beam having an incident ion flux of from about 0.5 to about             1,000,000 nA/mm², and most preferably said ion beam having             an incident ion flux of from about 0.5 to about 900,000             nA/mm²;         -   (iv) said at least a portion of said coated substrate's             pattern illumination-based annealed chemical coating's ion             beam irradiation treatment temperature being from about             0° C. to about 1,500° C., preferably said at least a portion             of said coated substrate's pattern illumination-based             annealed chemical coating's ion beam irradiation treatment             temperature being from about 5° C. to about 1,000° C., more             preferably said at least a portion of said coated             substrate's pattern illumination-based annealed chemical             coating's ion beam irradiation treatment temperature being             from about 5° C. to about 900° C., most preferably said at             least a portion of said coated substrate's pattern             illumination-based annealed chemical coating's ion beam             irradiation treatment temperature being from about 18° C. to             about 700° C.; and         -   (v) said at least a portion of said coated substrate's             pattern illumination-based annealed chemical coating's ion             beam irradiation exposure time to said ion beam being from             about 0.001 seconds to about 10,000,000 seconds, preferably             said at least a portion of said coated substrate's pattern             illumination-based annealed chemical coating's ion beam             irradiation exposure time to said ion beam being from about             0.01 seconds to about 1,000,000 seconds, more preferably             said at least a portion of said coated substrate's pattern             illumination-based annealed chemical coating's ion beam             irradiation exposure time to said ion beam being from about             0.1 seconds to about 100,000 seconds, most preferably at             least a portion of said coated substrate's pattern             illumination-based annealed chemical coating's ion beam             irradiation exposure time to said ion beam being from about             0.1 seconds to about 10,000 seconds; Sensor surface is a             means to generate sulfur vacancies     -   d.) electron beam illumination comprising at least a portion of         said coated substrate's pattern illumination-based annealed         chemical coating to an electron dose of from about 10²         electrons/nm² to about 10²⁵ electrons/nm², preferably from about         10³ electrons/nm² to about 10²² electrons/nm², more preferably         from about 10⁴ electrons/nm² to about 10²⁰ electrons/nm², most         preferably from about 10⁵ electrons/nm² to about 10¹⁸         electrons/nm² by exposing said at least a portion of said coated         substrate's pattern illumination-based annealed chemical coating         to:         -   (i) to an electron beam having an incident electron energy             of from about 0.1 eV to about 100,000,000 eV, preferably             said electron beam having an incident electron energy of             from about 1 eV to about 10,000,000 eV, more preferably said             electron beam having an incident electron energy of from             about 1 eV to about 1,000,000 eV, most preferably said             electron beam having an incident electron energy of from             about 1 eV to about 500,000 eV;         -   (ii) said at least a portion of said coated substrate's             pattern illumination-based annealed chemical coating's             electron beam illumination exposure time to said electron             beam illumination being from about 0.001 seconds to about             10,000,000 seconds, preferably said at least a portion of             said coated substrate's pattern illumination-based annealed             chemical coating's electron beam illumination exposure time             to said electron beam illumination being from about 0.01             seconds to about 1,000,000 seconds, more preferably said at             least a portion of said coated substrate's pattern             illumination-based annealed chemical coating's electron beam             illumination exposure time to said electron beam             illumination being from about 0.1 seconds to about 100,000             seconds, most preferably at least a portion of said coated             substrate's pattern illumination-based annealed chemical             coating's electron beam illumination exposure time to said             electron beam illumination being from about 0.1 seconds to             about 10,000 seconds;         -   (iii) said at least a portion of said coated substrate's             pattern illumination-based annealed chemical coating's             electron beam illumination treatment temperature being from             about 0° C. to about 1,500° C., preferably said at least a             portion of said coated substrate's pattern             illumination-based annealed chemical coating's electron beam             illumination treatment temperature being from about 5° C. to             about 1,000° C., more preferably said at least a portion of             said coated substrate's pattern illumination-based annealed             chemical coating's electron beam illumination treatment             temperature being from about 5° C. to about 900° C., most             preferably said at least a portion of said coated             substrate's pattern illumination-based annealed chemical             coating's electron beam illumination treatment temperature             being from about 18° C. to about 700° C.; Electron beam             illumination is a means of inducing surface changes on said             at least a portion of said coated substrate's pattern             illumination-based annealed chemical coating. Such changes             improve and/or control sites for physical and/or chemical             bonding.     -   e.) thermal annealing said at least a portion of said coated         substrate's pattern illumination-based annealed chemical         coating, said at least a portion of said coated substrate's         pattern illumination-based annealed chemical coating's thermal         annealing treatment temperature being from about 0° C. to about         1,500° C., preferably said at least a portion of said coated         substrate's pattern illumination-based annealed chemical         coating's thermal annealing treatment temperature being from         about 5° C. to about 1,000° C., more preferably said at least a         portion of said coated substrate's pattern illumination-based         annealed chemical coating's thermal annealing treatment         temperature being from about 5° C. to about 900° C., preferably         said at least a portion of said coated substrate's pattern         illumination-based annealed chemical coating's thermal annealing         treatment temperature being from about 18° C. to about 700° C.;     -   f.) chemically etching said at least a portion of said coated         substrate's pattern illumination-based annealed chemical coating         comprising contacting said at least a portion of said coated         substrate's pattern illumination-based annealed chemical coating         with an etching composition, preferably said coated substrate's         pattern illumination-based annealed chemical coating is treated         in accordance with at least one of the process of Paragraph         0049 a) or Paragraph 0049 b) prior to said contact with said         etching composition, preferably said etching composition is a         solution, gel or paste, more preferably said etching composition         is a solution having an etching concentration of from about         0.00003 mol/L to about 30 mol/L, more preferably said etching         composition is a solution having an etching concentration of         from about 0.0003 mol/L to about 25 mol/L, more preferably said         etching composition is a solution having an etching         concentration of from about 0.003 mol/L to about 20 mol/L, most         preferably said etching composition is a solution having an         etching concentration of from about 0.03 mol/L to about 20         mol/L; said contacting occurring for a time of from about 0.001         seconds to about 10,000,000 seconds, preferably said contacting         occurring for a time of from about 0.01 seconds to about         1,000,000 seconds, more preferably said contacting occurring for         a time of from about 0.1 seconds to about 100,000 seconds, and         most preferably said contacting occurring for a time of from         about 0.1 seconds to about 10,000 seconds, said etching         composition having a temperature over said contacting time of         from about 0° C. to about 200° C., preferably said etching         composition having a temperature over said contacting time of         from about 5-180° C., more preferably said etching composition         having a temperature over said contacting time of from about         10° C. to about 150° C., most preferably said etching         composition having a temperature over said contacting time of         from about 18° C. to about 100° C. While not being bound by         theory, Applicants believe that sulfur and/or selenium vacancies         in MoS₂ are produced via chemical modification by etching MoS₂         in a solution such as sodium hypochlorite (NaClO) solution as         provided above.     -   g.) electro-chemically treating said at least a portion of said         coated substrate's pattern illumination-based annealed chemical         coating by contacting said at least a portion of said coated         substrate's pattern illumination-based annealed chemical coating         with a chemical composition comprising an electrolyte and         subjecting said contacted at least a portion of said coated         substrate's pattern illumination-based annealed chemical coating         and said chemical composition comprising an electrolyte to an         electrical current, preferably at least a portion of said coated         substrate's pattern illumination-based annealed chemical coating         is subjected to said electrical current for a time of from about         0.01 seconds to about 60,000 seconds, more preferably at least a         portion of said coated substrate's pattern illumination-based         annealed chemical coating is subjected to said electrical         current for a time of from about 0.1 seconds to about 6,000         seconds, more preferably at least a portion of said coated         substrate's pattern illumination-based annealed chemical coating         is subjected to said electrical current for a time of from about         1 seconds to about 600 seconds, most preferably at least a         portion of said coated substrate's pattern illumination-based         annealed chemical coating is subjected to said electrical         current for a time of from about 10 seconds to about 60 seconds,         preferably said at least a portion of said coated substrate's         pattern illumination-based annealed chemical coating's         temperature is from about 0° C. to about 200° C. during said         time, preferably said at least a portion of said coated         substrate's pattern illumination-based annealed chemical         coating's temperature is from about 5° C. to about 180° C.         during said time, more preferably said at least a portion of         said coated substrate's pattern illumination-based annealed         chemical coating's temperature is from about 10° C. to about         150° C. during said time, most preferably said at least a         portion of said coated substrate's pattern illumination-based         annealed chemical coating's temperature is from about 18° C. to         about 100° C. during said time, preferably said electrolyte's         concentration is from about 0.0005M to about 50 M, more         preferably said electrolyte's concentration is from about 0.005M         to about 25M, more preferably said electrolyte's concentration         is from about 0.05M to about 20M, most preferably said         electrolyte's concentration is from about 0.5M to about 10M,         preferably said electrical current has a linear sweep         voltammetry sweeping speed of from about 0.001 mV s⁻¹ to about         500 mV s⁻¹, more preferably said electrical current has a linear         sweep voltammetry sweeping speed of from about 0.01 mV s⁻¹ to         about 250 mV s⁻¹, more preferably said electrical current has a         linear sweep voltammetry sweeping speed of from about 0.1 mV s⁻¹         to about 200 mV s⁻¹, most preferably said electrical current has         a linear sweep voltammetry sweeping speed of from about 1 mV s⁻¹         to about 200 mV s⁻¹. For example, the desulfurization of         multilayer MoS₂ samples is achieved by electro-chemical         desulfurization conducted in an electrochemical cell with 0.5 M         sulfuric acid (H₂SO₄).     -   h.) surface physical modification of at least a portion of said         coated substrate's pattern illumination-based annealed chemical         coating including but not limited to ball milling or polishing.

Applicants disclose a process of making a sensor according to paragraphs thirty-seven through fifty-six wherein each target is independently a chemical target or a biological target.

Sensor Comprising Pattern Illumination-Based Annealed Coated Substrate and One or More Functional Molecules and Method of Use

For purposes of this specification, headings are not considered paragraphs and thus this paragraph is paragraph fifty-eight of the present specification. The individual number of each paragraph above and below this paragraph can be determined by reference to this paragraph's number. In this paragraph fifty-eight, Applicants disclose a sensor comprising a pattern illumination-based annealed, coated substrate comprising a substrate having a first side and a second side and one or more types of functional molecules and/or one or more complexes comprising one or more types of functional molecules and one or more target molecules attached to at least a portion of said pattern illumination-based anneal coated substrate,

-   -   a.) said substrate's first side comprising;         -   (i) one or more coatings of patterned electrical conductive             material disposed over said substrate's first side,             preferably said patterned electrical conductive material             comprises a material selected from the group consisting of             poly(3,4-ethylenedioxythiophene),             poly(3,4-ethylenedioxythiophene) polystyrene sulfonate,             poly(pyrrole), polycarbazoles, polyindoles, polyazepines,             Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au, Ag, Cu, and Pt and             mixtures thereof; more preferably said patterned electrical             conductive material comprises a metal selected from the             group consisting of Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au,             Ag, Cu, and Pt and mixtures thereof, most preferably said             metal comprises a metal selected from the group consisting             of Mo, Cr, Ti, Au and mixtures thereof, most preferably said             one or more coatings of patterned electrical conductive             material is a coating of Mo, a coating of Cr and a second             coating of Au over said coating of Cr or a coating of Ti and             a second coating of Au over said coating of Ti; and         -   (ii) one or more chemical coatings disposed over said one or             more coatings of patterned electrically conductive material,             said one or more chemical coatings each independently             comprising a transition metal and an element selected from             the group consisting of hydrogen, carbon, nitrogen, oxygen,             sulfur, selenium, phosphorous and mixtures thereof,             preferably said one or more chemical coatings each             independently comprises a transition metal and an element             selected from the group consisting of oxygen, sulfur,             selenium and mixtures thereof, said one or more chemical             coatings each independently comprising at least one of an             amorphous, nanocrystalline, microcrystalline or crystalline             region, preferably said chemical coatings comprises one or             more transition metal dichalcogenides, preferably said one             or more transition metal dichalcogenides are selected from             the group consisting of MoS₂, W₅₂, MoSe₂, WSe₂, and mixtures             thereof, at least a portion of said one or more chemical             coatings being a pattern illumination-based annealed             chemical coating;     -   b.) said substrate's second side optionally comprising:         -   (i) one or more coatings of patterned electrical conductive             material disposed over said substrate's first side,             preferably said patterned electrical conductive material             comprises a material selected from the group consisting of             poly(3,4-ethylenedioxythiophene),             poly(3,4-ethylenedioxythiophene) polystyrene sulfonate,             poly(pyrrole), polycarbazoles, polyindoles, polyazepines,             Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au, Ag, Cu, and Pt and             mixtures thereof; more preferably said patterned electrical             conductive material comprises a metal selected from the             group consisting of Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au,             Ag, Cu, and Pt and mixtures thereof, most preferably said             metal comprises a metal selected from the group consisting             of Mo, Cr, Ti, Au and mixtures thereof, most preferably said             one or more coatings of patterned electrical conductive             material is a coating of Mo, a coating of Cr and a second             coating of Au over said coating of Cr or a coating of Ti and             a second coating of Au over said coating of Ti; and         -   (ii) one or more chemical coatings disposed over said one or             more coatings of patterned electrical conductive material,             said one or more chemical coatings each independently             comprising a transition metal and an element selected from             the group consisting of hydrogen, carbon, nitrogen, oxygen,             sulfur, selenium, phosphorous and mixtures thereof,             preferably said one or more chemical coatings each             independently comprises a transition metal and an element             selected from the group consisting of oxygen, sulfur,             selenium and mixtures thereof, said one or more chemical             coatings each independently comprising at least one of an             amorphous, nanocrystalline, microcrystalline or crystalline             region, preferably said chemical coatings comprises one or             more transition metal dichalcogenides, preferably said one             or more transition metal dichalcogenides are selected from             the group consisting of MoS₂, W₅₂, MoSe₂, WSe₂ and mixtures             thereof, at least a portion of said optional one or more             chemical coatings being a pattern illumination-based             annealed chemical coating. As used herein target molecules             can be simple molecules or macromolecules including but not             limited to proteins, lipids, and carbohydrates, target             molecules include aromatics, aromatic halogens, halocarbon,             polar aprotics, volatile organic compounds, hazardous gases,             for example, arsenic, radon, nitrogen dioxide, carbon             monoxide, carbon dioxide, carbon disulfide, ammonia,             napthalene, isoprene, terpenes, methanol, benzyl chloride,             hexachloro-1,3-butadiene, tribomomethane, 1,4-dioxane.

Applicants disclose a sensor according to paragraph fifty-eight comprising at least one of:

-   -   a.) at least one chemical coating comprising two or more regions         that are amorphous, nanocrystalline, microcrystalline or         crystalline with the proviso that at least two of said regions         are not identical with respect being amorphous, nanocrystalline,         microcrystalline or crystalline, at least two of said regions         being pattern illumination-based annealed via different pattern         illumination-based annealing processes; or     -   b.) at least one chemical coating comprising at least one region         that is amorphous, nanocrystalline, microcrystalline or         crystalline said at least one region being pattern         illumination-based annealed two or more times. The sensor of         Paragraphs fifty-eight and fifty-nine could be produced in         accordance with the processes of Paragraphs thirty-seven through         fifty-seven.

Applicants disclose a sensor according to paragraphs fifty-eight through sixty wherein:

-   -   a.) said substrate of said coated substrate is selected from         glass, polymer and mixtures thereof, preferably said polymer is         selected from the group consisting of polyethylene naphthalate,         polyimide, polycarbonate, polyethylene naphthalate and mixtures         thereof.     -   b) said one or more coatings of patterned electrical conductive         material is a coating of Mo, a coating of Cr and a second         coating of Au over said coating of Cr or a coating of Ti and a         second coating of Au over said coating of Ti; and     -   c) said one or more chemical coatings comprises a material         selected from the group consisting of MoS₂, WS₂, MoSe₂, WSe₂ and         mixtures thereof.

Applicants disclose a sensor according to paragraphs fifty-eight through sixty wherein said one or more functional molecules are biomaterials selected from the group consisting of peptides, nanozymes, proteins, lipids, carbohydrates and lectins, nucleic acids and mixtures thereof; preferably said biomaterial is selected from the group consisting of peptides, proteins, nucleic acids and mixtures thereof; preferably

-   -   a) said peptides are selected from the group consisting of         assemblies of the 20 most common amino acids interacting with         both target analytes and the sensor surface, and mixtures         thereof. Such interactions may occur via one or a combination of         the mechanisms of hydrogen bonding, Van der Waals forces, and         ionic interactions between charged species. Peptides may         interact with or bind to the sensor surface without         modification, such as the 12-mer peptide having SEQ. ID 1         discovered via peptide panning on the MoS₂ surface.         Alternatively, amino acids or other molecules may be added to         the peptide to promote binding to sensor surfaces or target         molecules for detection, such as the peptide having SEQ. 2         demonstrating enhanced interactions that may include binding to         laser-processed MoS₂ surfaces when terminated with two Leucine         amino acids. Expected trends dictating interaction strength and         even binding of amino acids in peptides to surfaces, such as         hydrophobicity, charge and surface contact, are not always         observed in practice due to changes in conformation when bound         and other factors. Peptides interacting with the sensor surface         may reduce the strength and frequency of nonspecific         interactions with samples containing multiple components and may         also chemically stabilize the sensor surface. Peptides         complementing receptor binding sites for elements of         cell-surfaces, transmembrane proteins, antibodies, and enzymes         provide a means of rapid, inexpensive, and stable         functionalization. For example, the peptide having SEQ. 2 is         known to bind to cardiac troponin (cTnI), which is regarded as a         biomarker for heart tissue damage. When the peptide is         functionalized with two leucine amino acids, binds to both the         laser-processed MoS₂ sensor surface and cTnI. Peptide binding to         targets of interest may include families of peptides bearing a         resemblance to binding regions of monoclonal antibodies. For         medical diagnostics, another peptide having SEQ. ID 3, is known         to bind to alanine aminotransferase, regarded as a biomarker for         liver damage. Additional examples of peptides interacting with         biological targets of interest may include the peptide having         SEQ. ID 4 detecting HIV1 protease, the peptide having SEQ ID 5         detecting trypsin, the peptide having SEQ. ID 6 for detection of         Caspase 3, and the peptide having SEQ. ID 7 for detection of         MMP-7.     -   b.) said nanozymes are selected from the group consisting of         nanomaterials with intrinsic enzyme-like characteristics,         mimicking the catalytic activity of peroxidase, oxidase,         catalase, haloperoxidase, glutathione peroxidase, uricase,         methane monooxygenase, hydrolase, and superoxide         dismutasegenerally in the form of compound nanoparticles,         including Fe₃O₂, Mn₃O₄, C₁₈Fe₇N₁₈, and mixtures thereof;     -   c.) said proteins are selected from the group consisting of         antibodies, antibody fragments, antibody mimics, single domain         antibodies, and enzymes and mixtures thereof; amino acids or         other molecules may be added or subtracted from these proteins         to promote interactions including binding to sensor surfaces.         Amino acids or other molecules may also be attached or removed         from these proteins to promote interactions between the proteins         and the sensor surface such as binding, or molecules may be         attached to sensor surface to promote interactions including         binding. Fundamental constituents of the 5 types of antibodies         may be digested into fragments to produce fragments interacting         with sensor surfaces allowing maintenance of the binding region         conformation for the desired effect of reducing non-specific         interactions with a sample. Additionally, smaller proteins with         characteristics allowing specific binding to target         biomolecules, analogous to whole antibodies or antibody         fragments, may be modified to interact with sensor surfaces or         the sensor surfaces may modified to interact with antibodies.         Proteins such as antibodies or antibody fragments interacting         with the sensor surface may reduce the strength and frequency of         non-specific interactions with samples containing multiple         components and may also chemically stabilize the sensor surface.         Such interactions may occur via one or a combination of the         mechanisms of covalent bonding, hydrogen bonding, Van der Waals         forces, and ionic interactions between charged species. This         approach of functionalizing sensor surfaces with antibodies or         antibody fragments is suitable for antibodies that bind to         surface proteins on viruses (such as SARS-CoV2, and Influenza         A), bacteria (such as Streptococcus pyogenes), and other         substances such as hormones (such as human chorionic         gonadotropic hormone) and proteins native to the body (e.g.,         cardiac troponin, cTnI) and substances foreign to the body (such         as THC, narcotics). Since antibodies for each of these         substances share the same fundamental structural elements for         digestion into fragments and use on illumination-crystallized         MoS₂ sensor surfaces. Enzymes are another biomolecule suitable         for promotion of specific interactions. For example, the         angiotensin-converting enzyme 2 (ACE2) binds to spike proteins         of the SARS-CoV and SARS-CoV-2 virus. Modification of ACE2         enzyme for strengthening interactions between the enzyme and the         MoS₂ sensor surface could involve attachment of amino acids         and/or other molecules to allow binding to both sensor and         target analyte. Modification could also involve removal of amino         acids and molecules until a region suitable for binding to the         target analyte remains. For electronic sensing, smaller binding         molecules generally lead to higher sensitivity, indicating an         advantage to using smaller molecules.     -   d.) said lipids are selected from the group consisting of lipid         bilayer arrays and liposomes and mixtures thereof including         those used for support of membrane proteins for biosensing     -   e.) said carbohydrates and lectins are selected from the group         consisting of natural carbohydrates including monosaccharides,         oligosaccharides, polysaccharides, or glycoconjugates with         proteins and lipids including glycoproteins, glycolipids, or         proteoglycans, glycosyltransferases and glycosidases and         mixtures thereof; and)     -   f.) said nucleic acids are selected from the group consisting of         deoxyribonucleic acid, ribonucleic acid and mixtures thereof to         identify genes and genetic mutations in healthy and diseased         tissue and other biomolecular targets.

Applicants disclose a sensor according to paragraphs fifty-eight through sixty-one wherein said one or more functional molecules' attachment to said pattern illumination-based anneal coated substrate comprises at least one of a covalent bond, electrostatic bond or a covalent and electrostatic bond. In one aspect, said at least one covalent bond comprises a disulfide bond.

Applicants disclose a sensor according to paragraphs fifty-eight through sixty-two wherein said one or more functional molecule's concentration on said pattern illumination-based anneal coated substrate is from about 0.001 nanograms per square centimeter to about 1,000 nanograms per square centimeter, preferably said one or more functional molecule's concentration on said pattern illumination-based anneal coated substrate is from about 0.01 nanograms per square centimeter to about 500 nanograms per square centimeter, more preferably said one or more functional molecule's concentration on said pattern illumination-based anneal coated substrate is from about 0.1 nanograms per square centimeter to about 200 nanograms per square centimeter, most preferably said one or more functional molecule's concentration on said pattern illumination-based anneal coated substrate is from about 0.1 nanograms per square centimeter to about 100 nanograms per square centimeter. The preferred concentration of biomaterial may depend on the geometry and desired sensitivity limit of the sensor device. For example, a smaller sensor geometry can be used to reduce the number of interactions with a species in the applied sample over a given time period to be reduced.

Applicants disclose a method of using a sensor according to paragraphs fifty-eight through sixty-three comprising the steps of:

-   -   a.) measuring one or more optical and/or electrical properties         of a sensor according to paragraphs fifty-five through sixty         after said sensor comprises one or more complexes comprising one         or more types of functional molecules and one or more target         molecules     -   b.) comparing said one or more optical and/or electrical         properties of said sensor to a baseline of said sensor measured         before said sensor comprises one or more complexes comprising         one or more types of functional molecules and one or more target         molecules. The response of the sensor to a biological sample may         be measured electrically or optically, or both electrically and         optically. Sensor responses indicating presence of a target         species may include changes in electrical resistance in a         chemresistor configuration, changes in current flow for a         transistor configuration, changes in refractive index, changes         in photoluminescence intensity or frequency, and other         electrical, optical, or combined electrical and optical         responses. After testing, the sample can be neutralized,         disposed of, recycled, regenerated, and/or reused. The complexes         comprising said one or more types of functional molecules and         one or more target molecules can from in a time from about 0.001         seconds to about 5,000,000 seconds, preferably the complexes         comprising said one or more types of functional molecules and         one or more target molecules can from in a time from about 0.1         seconds to about 5,000 seconds; and more preferably the         complexes comprising said one or more types of functional         molecules and one or more target molecules can from in a time         from about 0.1 seconds to about 1,000 seconds.

Suitable amorphous, nanocrystalline, microcrystalline and/or crystalline materials comprising a transition metal and hydrogen, carbon, nitrogen, oxygen, sulfur, selenium, tellurium, and/or phosphorous can be obtained from Plasmaterials (2268 Research Drive, Livermore, Calif. 94550 USA) and Kurt Lesker (1925 Route 51, Jefferson Hills, Pa. 15025 USA.

Patterned metal on silicon or glass wafers can be obtained from Sil'tronix (382 rue Louis Rustin, Technopole d'Archamps, 74160 Archamps, France) or University Wafer (11 Elkins Street, Unit 330, South Boston, Mass. 02127). Patterned metal on polymer substrates, including polyimide, polycarbonate, polyethylene naphthalate and polyethylene terephthalate may be obtained from VAST Films LTD (13525 Youngstown-Pittsburgh Rd, Petersburg, Ohio 44454). Peptides may be obtained from Genscript Corporation (860 Centennial Ave. Piscataway, N.J. 08854, USA). Antibodies and antibody fragments may be obtained from Virusys Corporation (6370 Keysville Road, Keymar, Md. 21757. Single-domain antibodies may be obtained from NanoTag Biotechnologies (Rudolf-Wissell-Straße 28a, 37079 Göttingen, Germany). Nanoparticles functioning as nanozymes can be obtained millipore sigma (400 Summit Drive Burlington, Mass. 01803). Lipids and kits for making liposomes are also available from millipore sigma.

Suitable continuous wave lasers for conducting Applicants can be obtained from Thorlabs (56 Sparta Avenue, Newtown, N.J. 07860 USA), Coherent (5100 Patrick Henry Dr., Santa Clara, Calif. 95054 USA), and TLM Laser Ltd (Navigation Court, Harris Business Park, Stoke Prior, Bromsgrove, Worcestershire, B60 4FD UK). Pulsed lasers suitable for the applications described here include the Keyence MDX series of laser models obtained from Keyence Corporation (720 South Colorado Boulevard, Suite 650-S Denver, Colo. 80246A) which is capable of a selected range of pulse lengths between microseconds to milliseconds. Lasers with femtosecond and picosecond pulse widths suitable for the applications described here are available from Control Micro Systems (CMS) Laser (4420-A Metric Drive Winter Park, Fla. 32792), Lamps with characteristics suitable for the applications described here include the Pulse Forge 3300 model by manufactured by Novacentrix. (400 Parker Dr. Suite 1110, Austin, Tex.). Suitable Raman spectrometer detectors can be acquired for Renishaw (764 McEwen Rd., Dayton, Ohio 45459 USA). Suitable optical detectors can be acquired from Horiba Scientific (1002 Harvest Ct., Coraopolis, Pa. 15108).

Examples

The following examples illustrate particular properties and advantages of some of the embodiments of the present invention. Furthermore, these are examples of reduction to practice of the present invention and confirmation that the principles described in the present invention are therefore valid but should not be construed as in any way limiting the scope of the invention.

Example 1: Laser Written resistor and capacitor in thin film molybdenum disulfide. A molybdenum disulfide (MoS₂) thin film of thickness totaling 900±50 nm was deposited onto a metal patterned glass or SiO₂ wafer via magnetron sputtering using a 99.95% pure MoS₂ target and Ti/Au contacts. The direct laser writing of resistors and capacitors was possible using a 514 nm laser and creating conducting MoO₂ patterns and insulating MoO₃ isolation with the Ti/Au contacts. The resistance can be controlled in a resistor component by varying the length of conductive material within the amorphous material, with the required MoO₃ isolation surrounding. Additionally, comb capacitors shown with tailored electronic properties are possible via patterning of the same materials but in different configurations.

Example 2: Gas sensor laser written in molybdenum disulfide Active circuit elements were also possible using the laser writing technique by taking advantage of the on/off properties of semiconducting 2H—MoS₂. One example of this is the laser writing of a chemresistor style gas sensor that can detect ammonia at sub 10 ppm levels. This chemresistor was composed of a semiconducting crystalline MoS₂ channel, metallic contact pads and electrodes, and a MoO₃ boundary isolation and was demonstrated to detect 10, 100, and 1000 parts per million of NH₃ gas.

Example 3: The first five materials listed in Column 4 of Table 1 below were made in accordance with Applicants' process on metallic contacts using a laser and then the same results were obtained using a lamp. Such materials are useful as listed in Column 5 of Table 1. The last 6 materials listed in Column 3 of Table 1 below are made in accordance with Applicants' process using a laser and then the same results were obtained using a lamp. Such materials are useful as listed in Column 5 of Table 1. The Examples in Table 1 row 1, 2, 5, 9 and 10 of column 4 show a crystalline structure changes in the starting material as represented by 2H, 1T, T-Phase and H-Phase while Examples in Table 1 row 3, 4, 6, 7, 8 and 9 of column 4 show a chemical change in the starting material.

TABLE 1 Post-annealed Starting Material Fluid blanket Methodology material Use Amorphous Vacuum Crystallization 2H-MoS₂ Semiconductor MoS₂ Vacuum Crystallization IT-MoS₂ Conductor Oxygen gas Oxidation MoO₂ Conductor (Shorter annealing time) Oxygen gas Oxidation MoO₃ Insulator (longer annealing time) Amorphous WS₂ Vacuum Crystallization 2H-WS₂ Semiconductor Amorphous TiS Oxygen gas Oxidation TiO Conductor Oxygen gas Oxidation TiO₂ Semiconductor Nitrogen gas Nitridization TiN Conductor Amorphous VS₂ Vacuum Crystallization T-phase VS₂ Insulator Vacuum Crystallization H-phase VS₂ Semiconductor Oxygen gas Oxidation VO₂ Insulator

Example 4. P-N junction with laser written MoS₂/WSe₂ Lateral P-N junctions are made possible through first deposition of metallic contacts followed by patterned amorphous deposition of in-plane heterjunctions of amorphous MoS₂/WSe₂ structures. With the use of one laser pass across the interface, a n-type semiconductor MoS₂ is in contact with a p-type WSe₂ semiconductor material, forming a P-N junction of use for light emitting diodes (LEDs) and other optical/electronic components.

Example 5: Sensor device with laser written MoS₂, patterned metal contacts and patterned ablated material. Multiplexed sensor devices require electrical isolation to ensure minimal cross-talk between laser written devices. With this in mind, laser patterned areas of crystallized MoS₂ were fabricated and the same laser was used to trace around the area that was annealed to remove all material within that region in creating an electrically isolated circuit. The ablation process removed in total about 1% area of the total MoS₂ film.

Example 6: Laser written chemical or biological sensor on e-beam evaporated patterned metal on glass substrate. A prepatterned metal film composed of gold or molybdenum metal in a pattern was first deposited on a glass substrate as depicted in FIG. 1 and FIG. 2 . A thin 3 nm molybdenum disulfide film is then sputter coated onto the glass/patterned metal substrate to form a continuous thin film. A CW laser is then utilized to crystallize the amorphous MoS₂ film to convert into semiconducting 2H—MoS₂ for sensing applications. The chemical sensor is then electrically isolated through laser ablation removal of the amorphous MoS₂ film around the crystallized 2H—MoS₂ to form a chem/bio sensor configuration.

Example 7: All laser written sensor on ablated metal pattern in roll-to-roll configuration. A roll-to-roll process is utilized to run a spool of flexible glass through a sputter-coater, laser processing system as depicted in FIG. 3 . First, a thin layer of molybdenum or gold metal is deposited over the entire glass substrate and the laser is used to ablate a pattern in such a configuration as identified in FIGS. 4-9 . The laser-ablated patterned metal film is then coated with 3 nm MoS₂ over the entire glass/metal substrate. Immediately following, a laser ablation step is used to remove all or some fraction of the amorphous MoS₂ except an area connecting the metal contacts, which is then laser annealed at a lower laser energy condition than that used for ablation to induce crystallization in a phase such as the hexagonal 2H—MoS₂ formation. The resultant devices are an embodiment of an all-laser fabrication roll-to-roll approach for chem/bio sensor fabrication. To monitor the degree and success of laser crystallization, a camera and Raman spectrometer was mounted in such a way to monitor the process at the main laser location. Additionally, to perform additional quality control, an optical light source and detector was mounted downstream to the process to evaluate broadband light transmission and absorption through the coated substrate.

Example 8: For direct binding of proteins, the sulfur chemistry of antibody fragments at their cysteine and proline-rich hinge region may be exposed via papain digestion to interact with the MoS₂ region of the sensor device which may have some concentration of atomic sulfur vacancies as shown in FIG. 10 . The presence of these vacancies may result in interactions that may include covalent or electrostatic binding of antibody fragments or some combination thereof.

Example 9: Addition of amino acids to a target-binding peptide for interaction of target binding peptide with sensor surface is shown in FIG. 11 . Two leucine amino acids are added to a c-TnI binding peptide. Interaction strength of the peptide with the sensor surface may be due in part to formation of a hydrophobic pocket with the leucine addition. Accumulation rates are shown for flowing solutions of two different peptide concentrations in a 1× concentration of phosphate buffered saline (PBS) on a MoS₂ surface. For the higher peptide concentration example, washing of the surface with 1× concentration phosphate buffer solution or doubly deionized water does not change the accumulated mass, suggesting strong interactions between the modified peptide and the MoS₂ substrate.

Example 10: A single chip with multiple sensors and antibody fragments applied for specific binding to a target analyte of interest is shown in FIG. 12 . On two sensor devices functionalized with influenza A HA protein monoclonal antibody fragments, concentrations of SARS-CoV2 spike protein (as indicated by the x axis) were applied and a much smaller sensor response was observed that at the same concentration of the complementary influenza HA analyte, demonstrating the utility of antibody functionalization for specific detection. The time response of the sensor is shown where a change in resistance is recorded within seconds of the application of the antibody fragments suggesting a rapid interaction once applied. The response time for application of the analyte is also shown to be within seconds which is expected for sensors with dimensions on the order of ˜100 micrometers.

Example 11: Thick MoS₂ with laser annealing and metal contacts occurring on or within the film to form 3D device. A thick (100 micrometers) amorphous film of MoS₂ is deposited onto a glass substrate with patterned metal contacts. A sensor device is laser annealed into the film occur in several stepwise procedures both at the surface of the film and within the depth. First, an area of the film outside of the active device area is laser ablated where the entirety of the film is removed in select areas. Within the remaining film, a focused nanosecond laser is used to crystallize the surface of MoS₂ (<1 micrometer) for the active region of the sensor, leaving the remaining 99% within the thickness unaltered. Then, a continuous wave laser is used to oxidize regions of the film through the entire thickness in order to form conductive MoO₃ to serve as isolation in a multiplex sensor device. Finally, a peptide molecule is attached to the laser treated crystallized MoS₂ region in order to operate as a biomolecular sensor selective to the antigen of interest.

Example 12: A laser system suitable for inducing ablation or transformations within a material may also have an integrated ‘sighting’ laser operated at a different wavelength, intensity, or both wavelength or intensity for determining the distance from the sample to the laser. The sighting laser may have a wavelength suitable for interrogation of materials structure, such as 633 nm for identification of resonant Raman peaks in MoS2 as the material is illuminated by the laser or after it interacts with the laser.

Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While the present invention has been illustrated by a description of one or more embodiments thereof and while these embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and process, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept. 

What is claimed is:
 1. A process of making a sensor or sensor array comprising: a.) pattern illumination-based annealing a coated substrate comprising a substrate having a first side and a second side, (i) said substrate's first side comprising; one or more coatings of patterned electrical conductive material disposed over said substrate's first side, said patterned electrical conductive material comprising a material selected from the group consisting of poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, poly(pyrrole), polycarbazoles, polyindoles, polyazepines, Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au, Ag, Cu, and Pt and mixtures thereof; and one or more chemical coatings disposed over said one or more coatings of patterned electrical conductive material, said one or more chemical coatings each independently comprising a transition metal and an element selected from the group consisting of hydrogen, carbon, nitrogen, oxygen, sulfur, selenium, phosphorous and mixtures thereof, said one or more chemical coatings each independently comprising at least one of an amorphous, nanocrystalline, microcrystalline or crystalline region; (ii) said substrate's second side optionally comprising one or more coatings of patterned electrical conductive material disposed over said substrate's first side, said patterned electrical conductive material comprising a material selected from the group consisting of poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, poly(pyrrole), polycarbazoles, polyindoles, polyazepines, Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au, Ag, Cu, and Pt and mixtures thereof; said one or more chemical coatings each independently comprising a transition metal and an element selected from the group consisting of hydrogen, carbon, nitrogen, oxygen, sulfur, selenium, phosphorous and mixtures thereof, said one or more chemical coatings each independently comprising at least one of an amorphous, nanocrystalline, microcrystalline or crystalline region; said pattern illumination-based annealing comprising using one or more lasers and/or lamps to achieve at least one of a chemical change or structural change in at least a portion of at least one of said one or more chemical coatings on at least one side of said substrate, and optionally the removal of at least a portion of said chemical coating on at least one side of said substrate; b.) optionally, attaching one or more types of functional molecules and/or one or more complexes comprising one or more types of functional molecules and one or more target molecules to at least a portion of said pattern illumination-based anneal coated substrate, said one or types of biomaterial being attached to: (i) a pattern illumination-based annealed portion of said pattern illumination-based anneal coated substrate; (ii) a portion of said pattern illumination-based anneal coated substrate that is not pattern illumination-based annealed; or (iii) a portion of said pattern illumination-based anneal coated substrate that is not pattern illumination-based annealed and a portion of said pattern illumination-based anneal coated substrate that is pattern illumination-based annealed; said process being a roll process wherein said coated chemically substrate is a rolled coated chemically substrate that is unrolled at least in part, said unrolled chemical coating portion of said coated substrate being at least in part pattern illumination-based annealed, said process comprising a quality control unit comprising one or more diagnostic detectors, said one or more diagnostic detectors positioned to collect light that has interacted with said one or more chemical coatings at the point of and/or after said pattern illumination-based annealing has occurred.
 2. A process of making a sensor according to claim 1 wherein said one or more diagnostic detectors are each independently an optical camera, an optical detector, or Raman spectrometer.
 3. A process of making a sensor according to claim 1 wherein said quality control unit comprises at least two diagnostic detectors, at least one of said diagnostic detectors positioned to collect light that has interacted with said one or more chemical coatings at the point of said pattern illumination-based annealing and at least one of said diagnostic detectors positioned to collect light that has interacted with said one or more chemical coatings after said pattern illumination-based annealing has occurred.
 4. A process of making a sensor according to claim 1 wherein said collected light that has interacted with said one or more chemical coatings at the point of and/or after said pattern illumination-based annealing has occurred is suppled prior to said interaction by a laser, an LED or a broadband light source.
 5. A process of making a sensor according to claim 1 wherein at least a portion of said collected light that has interacted with said one or more chemical coatings at the point of and/or after said pattern illumination-based annealing has occurred is suppled prior to said interaction by said one or more lasers and/or lamps used to achieve at least one of a chemical change or structural change in at least a portion of at least one of said one or more chemical coatings on at least one side of said substrate.
 6. A process of making a sensor according to claim 1 wherein said one or more functional molecules are biomaterials is selected from the group consisting of peptides, nanozymes, proteins, lipids, carbohydrates and lectins, nucleic acids and mixtures thereof.
 7. A process of making a sensor according to claim 1 wherein said biomaterial's attachment to said pattern illumination-based anneal coated substrate comprises at least one of a covalent bond, electrostatic bond or a covalent and electrostatic bond.
 8. A process of making a sensor according to claim 1 wherein said attaching said biomaterial's to said pattern illumination-based anneal coated substrate comprises contacting said at least a portion of said pattern illumination-based anneal coated substrate and said one or more types of biomaterials.
 9. A process of making a sensor according to claim 1 wherein: a) at least one of said one or more chemical coatings comprises two or more regions that are amorphous, nanocrystalline, microcrystalline or crystalline with the proviso that at least two of said regions are not identical with respect to being amorphous, nanocrystalline, microcrystalline or crystalline and said laser or lamp forms on, within or on and within said at least one of said one or more chemical coatings: (i) at least two electronic elements selected from a conductor, semiconductor and an insulator; (ii) two or more different conductors having at least one of the following: different electrical properties or different optical properties; (iii) two or more different semiconductors having at least one of the following: different electrical properties or different optical properties; or (iv) two or more different insulators having at least one of the following: different electrical properties or different optical properties;  said process being performed under one of the following conditions: vacuum of less 100 torr, air or under a fluid blanket other than air;  said pattern illumination-based annealing resulting in at least one of a chemical change or structural change, and the removal of at least a portion of at least one of said one or more chemical coatings and resulting in an electrical component, an optical component or a combined electrical and optical component being formed on, within or on and within at least a portion of said pattern illumination-based annealed one or more chemical coatings; or b) at least one of said one or more chemical coatings comprises at least one region that is amorphous, nanocrystalline, microcrystalline or crystalline, and said one or more lasers and/or lamps forms on, within or on and within said at least one of said one or more chemical coatings: (i) at least two electronic elements selected from a conductor, semiconductor and an insulator; (ii) two or more different conductors having at least one of the following: different electrical properties or different optical properties; (iii) two or more different semiconductors having at least one of the following: different electrical properties or different optical properties; or (iv) two or more different insulators having at least one of the following: different electrical properties or different optical properties;  said process being performed under one of the following environmental conditions: vacuum of less 100 torr, air or under a fluid blanket other than air, then repeating, one or more times said pattern illumination-based annealing on said portion of said one or more chemical coatings using one or more of the following: (i) the same device but at least one of the following: a different intensity or time; (ii) a different environmental condition from the previous environmental condition, said different environmental condition select from the same group of environmental conditions; or (iii) a lamp if the previous pattern illumination-based annealing was laser pattern illumination-based annealing or a laser if the previous pattern illumination-based annealing was lamp pattern illumination-based annealing  said pattern illumination-based annealing resulting in at least one of a chemical change or structural change, and the removal of at least a portion of at least one of said one or more chemical coatings and resulting in an electrical component, an optical component or a combined electrical and optical component being formed on, within or on and within at least a portion of said pattern illumination-based annealed one or more chemical coatings.
 10. The process of claim 9 wherein for element 5b) said at least one chemical coating comprises two or more regions that are amorphous, nanocrystalline, microcrystalline or crystalline with the proviso that at least two of said regions are not identical with respect being amorphous, nanocrystalline, microcrystalline or crystalline, at least two of said regions being pattern illumination-based annealed via different pattern illumination-based annealing processes.
 11. The process of claim 1 wherein said transition metal is selected from the group consisting of molybdenum, tungsten, niobium, tantalum, vanadium, titanium, chromium, iron, rhodium, hafnium, rhenium and mixtures thereof.
 12. The process of claim 1 wherein said process is performed under a fluid blanket other than air.
 13. The process of claim 1 wherein said fluid blanket comprises: a) an element selected from the group consisting of krypton, xenon, radon, argon, neon, helium, hydrogen, carbon, nitrogen, oxygen, sulfur, selenium, phosphorous and mixtures thereof; b) based on total fluid volume greater than 0% to about 19% or from 21% to 100% oxygen; and/or c) greater than 0% to about 78% or from 80% to 100% nitrogen.
 14. A process according to claim 1 wherein said material comprises at least one region that is amorphous or nanocrystalline.
 15. A process according to claim 1 wherein said pattern illumination-based annealing is achieved by using one or more lasers , said one or more lasers each being independently selected from a laser that is a pulsed laser, a continuous laser or a pulsed/continuous laser.
 16. A process according to claim 1 wherein said pattern illumination-based annealing is achieved by using a continuous wave laser to subject at least a portion of said chemical coating, for a time of about 0.001 milliseconds to 60 seconds to said continuous laser; said continuous laser having power of from about 1 microwatt to about 1 megawatt over the time period said at least a portion of said chemical coating is subjected to said continuous laser.
 17. A process according to claim 1 wherein said pattern illumination-based annealing is achieved by using a lamp to subject at least a portion of said chemical coating for a time of about 10 microseconds to about 500,000 microseconds to said lamp, said lamp having power of from about 0.01 J/cm²to about 1,000 J/cm².
 18. A process according to claim 1 wherein said pattern illumination-based annealing is achieved by using a pulsed laser to subject at least a portion of said chemical coating for a time of about 0.1 femtoseconds to 60 seconds to said pulsed laser; said pulsed laser having a peak power of from about 0.1 microwatt to about 1000 gigawatts over the time period said at least a portion of said chemical coating is subjected to said pulsed laser; said pulsed laser having a pulse period of about 0.1 femtoseconds to 1 second.
 19. The process of claim 1 wherein, said each chemical coating independently has a thickness of from about 0.1 nanometers to about 1 centimeter.
 20. The process of claim 1 wherein, said electrical and/or optical component is selected from the group consisting of an inductor, a capacitor, a resistor, a diode, a transistor, a trace, a battery, an optical filter, a chemical sensor, a biological sensor and a solar cell.
 21. The process of claim 1 wherein each of said one or more chemical coatings have an area and a thickness and said removal of said at least a portion of said one or more chemical coating occurs, said removal comprising at least one of: a.) laser ablation removal of from about 0.1% to about 99.9% of at least one of said one or more chemical coatings' area; or b.) laser ablation removal of at least 85% of at least one of said chemical coatings' thickness; or laser ablation removal of about 85% to about 99% of at least one of said chemical coatings' thickness.
 22. The process of claim 1 wherein said substrate of said coated substrate is selected from glass, polymer and mixtures thereof.
 23. The process of claim 1 wherein at least a portion of said coated substrate's pattern illumination-based annealed chemical coating is further treated by at least one of the following processes: a.) two or more pattern illumination-based annealings; b.) plasma treatment comprising exposing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an ionized gas derived from the group consisting of He, Ne, Ar, Kr, Xe, Hz, O₂, SF₆, CF₄, N₂ and mixtures thereof; (i) said plasma treatment being conducted at a pressure of from about 0.1 mTorr to about 1000 Torr; (ii) said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating's plasma treatment temperature being from about 0° C. to about 1,500° C.; and (iii) said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating exposure time being from about 0.001 seconds to about 10,000,000 seconds; c.) ion beam irradiation comprising exposing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an ion beam, said ion beam comprising an ionized gas derived from the group consisting of He, Ne, Ar, Kr, Xe, H₂, O₂, SF₆, CF₄, N₂ and mixtures thereof; (i) said ion beam having an incident ion energy of from about 50 eV to about 10,000 eV; (ii) said ion beam having an incoming ion species incident angle of from about 1° to 90°, relative to the surface being bombarded; (iii) said ion beam having an incident ion flux of from about 0.1 nA/mm² to about 900,000,000 nA/mm²; (iv) said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating's ion beam irradiation treatment temperature being from about 0° C. to about 1,500° C.; and (v) said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating's ion beam irradiation exposure time to said ion beam being from about 0.001 seconds to about 10,000,000 seconds; d.) electron beam illumination comprising at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an electron dose of from about 10² electrons/nm² to about 10²⁵ electrons/nm² by exposing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to: (i) to an electron beam having an incident electron energy of from about 0.1 eV to about 100,000,000 eV; (ii) said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating's electron beam illumination exposure time to said electron beam illumination being from about 0.001 seconds to about 10,000,000 seconds; (iii) said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating's electron beam illumination treatment temperature being from about 0° C. to about 1,500° C.; e.) thermal annealing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating, said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating's thermal annealing treatment temperature being from about 0° C. to about 1,500° C.; f.) chemically etching said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating comprising contacting said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating with an etching composition; g.) electro-chemically treating said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating by contacting said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating with a chemical composition comprising an electrolyte and subjecting said contacted at least a portion of said coated substrate's pattern illumination-based annealed chemical coating and said chemical composition comprising an electrolyte to an electrical current; h.) surface physical modification of at least a portion of said coated substrate's pattern illumination-based annealed chemical coating. 